Dye compositions comprising a fluorocarbon,pigment,bonding agent and dispersant

ABSTRACT

A FLUORINE CONTAINING POLYMER OF THE MONOMER RFP, WHERE P IS -OOCCR1=CH2 AND R1 IS H OR CH3, AND WHERE RF IS: R2(CF2)A(CH2)X-, WHERE R2 IS F OR H, A IS AN INTEGER BETWEEN 1 AND 20 AND X IS EITHER 1 OR 2, (CF3)2CR3(CF2)B(CH2)X-, WHERE R3 IS F OR H WHEN B IS 0, R3 IS F WHEN B IS AN INTEGER BETWEEN 1 AND 18 AND X IS EITHER 1 OR 2, OR R4 (C-C6F10)CH2-, WHERE R4 IS F OR CNF2N+1 AND N IS AN INTEGER BETWEEN 1 AND 4 AND WHERE C- DESIGNATES AN ALICYCLIC STRUCTURE, IS ADDED TO A DISPERSION CONTAINING A PIGMENT, A BONDING AGENT AND A DISPERSING AGENT TO OBTAIN IMPROVED DYE COMPOSITIONS.

United States Patent DYE COMPOSITIONS COMPRISING A FLUORO- CARBON, PIGMENT, BONDING AGENT AND DISPERSANT Melville W. Ulfner, Media, Pa., assignor to Air Products and Chemicals, Inc Philadelphia, Pa. No Drawing. Filed Aug. 19, 1970, Ser. No. 65,313 Int. Cl. C08f 45/66 US. Cl. 260-8 13 Claims ABSTRACT OF THE DISCLOSURE A fluorine containing polymer of the monomer R P, where P is -OOCCR,=CH and R is H or CH and where R is:

R ('CF ),,(CH where R is F or H, a is an integer between 1 and 20 and x is either 1 or 2; (CF3)2CR3(CF2)1)(CH2)X-, Where R3 IS F or H When I] is 0, R is F when b is an integer between 1 and 18 and x is either 1 or 2; or

R4 (cC F )CH Where R4 is F Or C F2 and I1 IS an integer between 1 and 4 and where c-- designates an alicyclic structure,

is added to a dispersion containing a pigment, a bonding agent and a dispersing agent to obtain improved dye compositions.

BACKGROUND OF THE INVENTION The present invention relates to compositions for dyeing textiles with insoluble pigments and more particularly, to the preparation of improved pad deying compositions obtained by the incorporation of certain fluorine containing polymers with a dispersion containing a pigment, a bonding agent and a dispersing agent.

conventionally, pigment dyeing systems consist of a dispersion of finely ground pigment and binder compound. One method of pad dyeing is to immerse the textile in a bath containing the pigment and binder compound and then pass the textile between squeeze rolls which remove the excess of color and other bath constituents. As an alternative method, one of the squeeze rolls is partially immersed in the color bath, whereby some of the bath is carried to the nip between the partially immersed roll and the roll adjacent to it. In the latter case, the textile is dyed by passing between the rolls without previous immersion in the bath. The amount of pigment in respect to the amount of resin binder employed will vary with the character of pigment and the depth of color desired. Properly applied, the pigment should impinge on the fabric surface with a minimum of excess binder resinpro tecting the surface. The process of pad dyeing with pigments has had serious drawbacks. One of these drawbacks is the fact that the pigment dyed textile may have what is described as poor appearance. In other words, the dyeing is uneven, showing dark areas and light areas in the textile material. This unevenness may be due to the migration of the pigment. Another drawback is the fact that the pigment dyed textile material does not have durability to dry cleaning and laundering.

Although fluorochemicals have been used to impart soil repellency characteristics to textiles and are in fact used commercially today for that purpose, it was unexpected to find that certain fluorochemicals can be incorporated into dye compositions to improve the uniformity of fabric 3,730,924 Patented May I, 1973 dyeing and to impart durability to the dye applied to the fabrics.

SUMMARY OF THE INVENTION An object of the present invention is to provide improved pad dyeing compositions and a method of preparing the same.

Another object of the present invention is to provide dye compositions, comprising certain fluorine containing polymers and a dispersion containing a pigment, bonding agent and dispersing agent, which provide uniformity of fabric dyeing and impart durability to the dye applied to the fabric.

Still another object of the present invention is to provide pad dyeing compositions having improved uniformity of fabric dyeing together with soil repellency and soil release characteristics.

These and other objects, advantages and features of the invention are obtained by the addition of 0.1 to 5 percent by Weight of a fluorine containing polymer prepared from the monomer R P, where P is OOCCR =CH and R is H or CH and where R is:

R (CF ),'(CH where R is F or H, a is an integer between 1 and 20 and x is either 1 or 2;

(CF CR (CF (CH where R is F or H when I; is 0 and R is F when b is an integer between 1 and 18 and x is either 1 or 2; or

R (c-C F )CH where R; is F or C F and n is an integer between 1 and 4 and where c designates an alicyclic structure,

to a dispersion containing a pigment, bonding agent and a dispersing agent. The resulting dye compositions not only permit fabrics to be dyed more uniformly, but impart durability to the dye applied to the fabric, such that the dye is more durable to more laundering. The dyeing compositions of the present invention also render the dyed fabric soil repellent.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a preferred embodiment of the invention, bonding agent is added to a dispersion of pigment and the total material is stirred until homogeneous. The dispersing agent, an aid in maintaining the pigment in a desirably dispersed state, is then added to the homogeneous material. For maximum pad bath stability, the bath is then adjusted to a pH equal to or greater than 8 by the addition of a base. Finally, the fluorine containing polymer is added and the resulting mixture is stirred until the composition is homogeneous. The resulting composition constitutes the bath which is used for padding fabric. Typically, the fabric is weighed before and after padding, and the pressure on the padding rolls is ajusted to yield the desired wet pickup of the composition.

The fluorine containing polymers employed in this invention are prepared from monomers having the structure R P, where P is OOCCR =CH and R is H or CH and where R is:

R (CF ),,(CH where R is F or H, a is an integer between 1 and 20 and x is either 1 or 2;

(CF CR (CF ,(CH where R is F or H when b is 0 and R is F when b is an integer between 1 and 18 and x is either 1 or 2; or

3 R (CC F )CH where R; is F or C F and n is an integer between 1 and 4 and where c-- designates an alicyclic structure. The following monomers are representative:

1 c designates an alicyclic structure.

All commercially available organic and inorganic pigments may be employed in the present invention. Such pigments include such natural organic pigments as fustic and tumeric; such synthetic organic pigments as indanthrene blues, naphthol yellows, azo reds and phthalocyanine greens; such natural inorganic pigments as umber, and ochre; such synthetic inorganic pigments as iron blues, chrome orange, cadmium reds, zinc whites, and iron oxide brown; and the like. Advantageously, the pigments employed will be inert with respect to the balance of the dye composition and be fast to light. In addition, the pigments should be non-bleeding, and unaffected by cleaning solutions and soaps. Based on the percent active weight to be deposited on the fabric, the amount of pigment employed can vary between 0.1 to 15 percent by weight of the fabric weight, with 2-10% being a preferred range.

For printing and dyeing of textiles, the usual procedure is to disperse the pigment particles in a liquid. An aqueous dispersion is preferred, but various non-aqueous systems, including alcohols, ketones, etc., can be employed.

The bonding agent utilized in the present invention can include any of the bonding agents normally employed in the art, such as urea formaldehyde, melamine formaldehyde, ethyl cellulose, mixtures of ethyl and butyl cellulose, carboxymethyl cellulose, ethylacrylate homopolymers and copolymers, methyl methacrylate homopolymers and copolymers, and the like. Specific examples of alkylated melamine formaldehyde condensation products which may be used in accordance with this invention include propylated methylol-melamine, butylated methylol-melamine, hexylated methylol-melamine, cyclohexylated methylolmelamine, etc. Preferably, the bonding agent constitutes a resin emulsion such as an acrylate emulsion containing at least one reactive pendant group, such as N-methylol acrylamide. Thus, both natural bonding agents, such as albumen and casein, and synthetic bonding agents, such as ethyl cellulose, hydroxyethyl cellulose and urea formaldehyde, can be employed. Prior to the present invention, the choice of the particular bonding was extremely critical since the fastness of pigment-dyed fabrics to washing, dry-cleaning, scrubbing and abrasion depended largely upon the type of bonding material employed. In fact, it was not uncommon to employ combinations of two or more types of bonding agents in order to attempt to obtain all of the desired characteristics. The present invention provides a marked improvement in this area in assisting in obtaining the desired characteristics while lessening the critical requirements of the bonding agent. Based on the percentage of active weight to be deposited on the fabric, between 1 to 20 percent of the bonding agent can be employed, with a preferred amount being in the range of about 4 to 10 percent.

The dispersing agent utilized in the present invention can be of the type normally employed in the art. It is not unknown to employ a material as the dispersing agent which in some formulation may serve as a bonding agent. Such additives may thus be carboxymethyl cellulose, hydroxyethyl cellulose, sodium lignosulfonate, sodium caseinate, or other. Particularly preferred is sodium alginate as the dispersing agent. The sodium alginate is typically added to the other ingredients as a dispersion of the sodium alginate in liquid such that, based on the percent of active weight to be deposited on the fabric, an effective amount between 0.025 and 2 percent of sodium alginate is employed, with the preferred amount being in the vicinity of 0.07 to 1.0 percent. Since the preferred dispersion system is an aqueous system, normally a dispersion of sodium alginate in water is added to the homo geneous aqueous dispersion of pigment and bonding agent.

In order to regulate the pH in a range equal to or greater than 8, aqueous ammonia is normally employed. However, any amine which can be volatilized at moderate temperatures can be employed. Such amines include ethylamine and isopropylamine.

Textile materials such as cotton fabrics, Dacron-cotton fabrics, polyester fabrics, rayon blends, nylon, Orlon, and similar textile materials are normally treated by running the textile material through a padding bath maintained at a temperature between about 65 F. and 180 F. Pickup of the padding composition is controlled by regulating the pressure of squeeze rolls to yield the desired wet pickup, e.g. about percent of the weight of the dry fabric being treated. Normally an adequate cure time for the treated fabric is 15 minutes at 325 F. Of course, the cure time can be shortened by elevating the temperature. The actual time and temperature used depend on the weight of the fabric and to a lesser degree on the depth of shade applied.

While the following examples illustrate the nature of the present invention, the invention is not intended to be limited to these specific embodiments.

Example I A dye composition of the following materials was prepared containing approximately 8.318 percent active weight of materials diluted to percent with water.

Materials: Percent active weight Green iron salt of nitrosobetanaphthol 0.700 Butylated melamine formaldehyde resin 5.900 Ethyl cellulose 0.450 Sodium alginate 0.088

Aqueous ammonia to pH 8. Homopolymer of the monomer C F CH OOCCH=CH 1.180

The above dye composition was padded onto a 65/35 unsized polyester/cotton fabric to deposit an 85 percent wet pickup, based on the weight of the fabric. Thus, 85 percent of the value shown under percent active weight in the above table was deposited on the fabric.

The fabric treated with the dye composition in the manner indicated above was compared to identical fabric similarly treated except for the absence of a fluorine containing polymer in the dye composition. It was found that the dyed fabric containing the fluorochemical was (1) dyed more uniformly, (2) that the dye was more durable to laundering, (3) that the dyed fabric showed improved soil repellency and soil release characteristics and (4) that the fabric showed high oil and water repellency.

A photoelectric reflection meter having a green tristimulus filter was employed to measure the percent reflectance of padded swatches to reveal the durability and soil release characteristics of both the control dye composition and the dye composition containing fluorine containing polymers in accordance with the present invention. In each instance, the padded swatches were cured in a gravity feed circulating hot air oven at 325 F. for 15 minutes and then allowed to equilibrate for 24 hours at 50 percent relative humidity at a temperature of 73 F. before testing commenced. Soiling of the padded swatches was made with the synthetic soil described in the article by J. M. Salsbury et al. entitled Soil Resistant Treatment of Fabrics in The American Dyestutf Reporter for Mar.

26, 1956. Laundering of soiled fabric swatches was done as described in AATCC Test Method 61, No. IHA, except that 0.2 percent Tide was employed and no sodium metasilicate was employed.

A 63 percent reflectance was obtained from both the control padded swatch and the padded swatch containing the fluorine containing polymers of the present invention. However, following one soiling and then washing by AATCC Test Method 61, No. IIIA, equivalent to five commercial washes, the percent reflectance of the control padded swatch fell to 44 percent, whereas, after one soiling and washing by the AATCC method the padded swatch-es prepared using the fluorine containing polymers of the present invention had a percent refiectancy of 56 percent. Even after repeating the soiling procedure and subjecting the samples to the second cycle of the AATCC wash cycle, equivalent to a total of commercial washes, the percent reflectancy of the padded swatches prepared in accordance with the present invention had a reflectance Example II A qualitative, visual analysis of the difference between padded, dyed fabric swatches containing no fluorine containing polymer and padded, dyed fabric swatches containing the fluorine containing polymers of the present invention can be clearly shown. For example, employing the composition of Example I, except using benzidine yellow as the pigment, the following results were obtained:

where R;, is F or H when b is 0 and R is F when b is an integer between 1 and 18 and x is either 1 or 2; or R4 (C "C6F10)CH2, Where R4 is F 01' C F2 +1 and Il is an integer between 1 and 4 and where cdesignates an alicyclic structure.

are added to a dispersion of pigment, bonding agent and dispersing agent the appearance of dyed textile is not only improved, but also the fastness properties of the dye imparted to the textile material is improved thus rendering the dye more durable to laundering. Moreover, the compositions of the present invention also render treated fabrics more soil repellent.

' If desired, known anti-soiling substances, such as aluminum silicate; preservatives, such as sodium benzoate or potassium sorbate; waterproofing agents, such as methylol stearamide and methylene-bis-stearamide; anti-static agents; heat stability additives; buffering agents, such as diammonium phosphate; etc. may be incorporated into the formulations of the present invention.

Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and therefore, only such limitations should be imposed as are indicated in the appended claims.

What is claimed is:

1. A pad dyeing composition consisting essentially of a fluoropolymer and a dispersion of a pigment, bonding agent and dispersing agent, said fluoropolymer having the structure:

wherein P is OOCCR =CH in which R is H or CH and where Rf is:

R (CF ),,(CH in which R is F or H, a is an integer of from 1 to 20 and x is either 1 or 2;

Two sailings One soiling, one and two wash Dye composition No soil, no wash wash cycle cycles Control Yellow, with white striations.-- Dirty yellow green. Olive. With fluorine containing polymer... Bright uniform yellow Bright yellow Bright yellow.

Example III Following the procedure of Example I, a dye composition is prepared substantially similar to that of Example I except the fluorine containing polymer material is the homopolymer of the monomer This dye composition is applied to 65/35 unsized polyester/cotton fabric at an 85 percent wet pickup, based on the weight of the fabric, to deposit 1% homopolymer on the fabric. Control samples are identical except for the absence of a fluorine containing polymer in the dye composition. The swatches, treated with the dye composition containing the fluorine containing homopolymer and employing the tests described in Example I, show results improved over the controls similar to those described in Example I, i.e., more uniformity of dyeing, greater durability in laundering, improved soil repellency and soil release characteristics, and improved oil and water repellency.

From the foregoing it will be seen that this invention is well adapted to obtain all of the ends and objects hereinabove set forth, together with other advantages which are obvious and which are inherent to the system. When the fluorine containing polymers prepared from monomers of the structure RfP, where P is OOCCR =CH and R is H or CH and where R; is:

R (CF ),,(CI-I where R is F or H, a is an integer between 1 and20 and x is either 1 or 2;

in which R is F or H when b is 0 and R is F when b is an integer of from 1 to 18 and x is either C l and n is an integer of from 1 to 4 and where c designates an alicyclic structure.

2. A method of making a pad dyeing composition consisting essentially of adding a bonding agent to a dispersion of pigment and stirring the bonding agent and pigment until a homogeneousmixture is obtained, adding a dispersing agent to the homogeneous mixture of bonding agent and pigment, adjusting the pH of the mixture to at least 8 and adding a fluoropolymer to the resulting mixture, said fluoropolymer having the structure:

RfP

wherein P is OOCCR =CH in which R is H or CH;,, and where R, is:

R (CF ),,(CH in which R; is F or H, a is an integer of from 1 to 20 and x is either 1 or 2;

in which R is F or H when b is 0 and R is F when b is an integer of from 1 to 18 and x is either 1 or 2; or R (c-C F )CH where R; is F or C F and n is an integer of from 1 to 4 and where cdesignates an alicyclic structure. 3. The composition of claim 1 wherein the dispersing agent is sodium alginate.

4. The method of claim 2 wherein the dye composition is diluted to 100 percent with water.

5. The method of claim 2 wherein the dispersing agent is sodium alginate.

6. The composition of claim 1 wherein the dispersing agent is present in an amount from about 0.025 to about 2% by weight.

7. The composition of claim 1 wherein the fluoropolymer is present in an amount from about 0.1 to about 5 percent by weight.

8. The composition of claim 1 wherein the pigment is present in an amount from about 0.1 to about 10 percent by weight.

9. The composition of claim 1 wherein the bonding agent is present in an amount from about 1 to about 20 percent by weight.

10. The composition of claim 1 wherein the fluoropolymer is a homopolymer of CqF15CH2OOCCH=CH2.

11. The method of claim 2 wherein the fluoropolymer is present in an amount from about 0.1 to about 5 percent by weight.

12. The method of claim 2 wherein the fiuoropolymer is a homopolymer of C 1 CH OOCCH=CH 13. The method of claim 2 wherein the fiuoropolymer is stirred until a homogeneous mixture is obtained.

References Cited UNITED STATES PATENTS 2,664,365 12/1953 La Piana et a1. 2608 X 3,068,187 12/1962 Bolstad et al. 26029.6 3,256,230 6/1966 Johnson et a1. 26029.6 3,277,039 10/1966 Marascia et al 26029.6 3,282,905 11/1966 Fasick et al. 26029.6 X 3,378,609 4/1968 Fasick et al. 26029.6 X 3,438,925 4/1969 Raynolds et al. 26029.6 X 3,462,296 8/1969 Raynolds et al. 26029.6 X 3,491,169 1/1970 Raynolds et a]. 26029.6 X 3,546,187 12/1970 Tandy 26029.6 X 3,138,481 6/1964 Arnold et a1. 26041 X 3,385,812 5/1968 Brachman 26029.6

HOWARD E. SCHAIN, Primary Examiner US. Cl. X.R.

8-21 C, 162 A, DIG. 7; 26017 R, 17.4 R, 29.4 UA, 29.6 F, 37 P, 37 R 

